ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-11665-2012 In situ measurements of volatile organic compounds in a boreal forest Hakola H. 1 Hellén H. 1 Hemmilä M. 1 Rinne J. 2 Kulmala M. 2 Finnish Meteorological Institute, P.O.Box 503, 00101 Helsinki, Finland Department of Physical Sciences, University of Helsinki, P.O. Box 68, 00014 University of Helsinki, Finland 06 12 2012 12 23 11665 11678 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/11665/2012/acp-12-11665-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/11665/2012/acp-12-11665-2012.pdf

We present biogenic VOC, including sesquiterpenes, measurements at the SMEAR II station (Station For Measuring Forest Ecosystem-Atmosphere Relations) in Finland using an in situ gas chromatograph mass-spectrometer with 2 h time resolution. The measurements were conducted over the period October 2010–October 2011, at least one week every month. To our knowledge there are no earlier species-speciated semi-continuous BVOC data also covering dormant periods. This was also the first time sesquiterpene mixing ratios were measured in a boreal forest. <br><br> During the winter months, and still in March, the mixing ratios of all biogenic compounds were very low, most of the time below detection limits. The monoterpene mixing ratios increased in April and started to show diurnal variability, with maximum mixing ratio at night and minima during the day. The diurnal variability continued until October, after which the mixing ratios decreased and then only occasional episodes took place. The diurnal variation was affected by boundary layer height. Sesquiterpene mixing ratios were very low, only a few ppt. The main sesquiterpenes were longifolene and isolongifolene. The diurnal variation of isoprene was opposite to the mono- and sesquiterpene diurnal curve due to isoprene's light dependent emissions. Due to its daytime maximum mixing ratios, isoprene also dominated hydroxyl radical reactivity in summer even though our isoprene measurements are underestimates due to a breakthrough in a cold trap.

 References Aaltonen, H., Pumpanen, J., Pihlatie, M., Hakola, H., Hellén, H., and Bäck, J.: Emissions of biogenic volatile organic compounds from boreal Scots pine forest floor, Agr. Forest Meteorol., 151, 682–691, 2011. Aaltonen, H., Pumpanen, J., Hakola, H., Vesala, T., Rasmus, S., and Bäck, J.: Snowpack concentrations and estimated fluxes of volatile organic compounds in a boreal forest, Biogeosciences Discuss., 9, 527–555, http://dx.doi.org/10.5194/bgd-9-527-2012doi:10.5194/bgd-9-527-2012, 2012. Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds. Journal of physical and chemical reference data, Monograph, 2, 216 pp., 1994. Bonn, B., Kulmala, M., Riipinen, I., Sihto, S.-L., and Ruuskanen, T.: How biogenic terpenes govern the correlation between sulphuric acid concentrations and new particle formation, J. Geophys. Res., 113, D12209, http://dx.doi.org/10.1029/2007JD009327doi:10.1029/2007JD009327, 2008. Bouvier-Brown, N. C., Goldstein, A. H., Gilman, J. B., Kuster, W. C., and de Gouw, J. A.: In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry, Atmos. Chem. Phys., 9, 5505–5518, http://dx.doi.org/10.5194/acp-9-5505-2009doi:10.5194/acp-9-5505-2009, 2009. Bäck, J., Aalto, J., Henriksson, M., Hakola, H., He, Q., and Boy, M.: Chemodiversity of a Scots pine stand and implications for terpene air concentrations, Biogeosciences, 9, 689–702, http://dx.doi.org/10.5194/bg-9-689-2012doi:10.5194/bg-9-689-2012, 2012. Ghirardo, A., Koch, K., Taipale, R., Zimmer, I., Schnitzler J.-P., and Rinne, J.: Determination of de novo and pool emissions of terpenes from four common boreal/alpine trees by $^13$CO<sub>2</sub> labeling and PTR-MS analysis, Plant, Cell Environ., 33, 781–792, http://dx.doi.org/10.1111/j.1365-3040.2009.02104.xdoi:10.1111/j.1365-3040.2009.02104.x, 2010. Haapanala, S., Hakola, H., Hellén, H., Vestenius, M., Levula, J., and Rinne, J.: Is forest management a significant source of monoterpenes into the boreal atmosphere?, Biogeosciences, 9, 1291–1300, http://dx.doi.org/10.5194/bg-9-1291-2012doi:10.5194/bg-9-1291-2012, 2012. Hakola, H., Tarvainen, V., Laurila, T., Hiltunen, V., Hellén, H., and Keronen, P.: Seasonal variation of VOC concentrations above a boreal coniferous forest, Atmos. Environ., 37, 1623–1634, 2003. Hakola, H., Hellén, H., and Laurila, T.: Ten years of light hydrocarbon (C<sub>2</sub>-C$_6)$ concentration measurements in background air in Finland, Atmos. Environ., 40, 3621–3630, 2006a. Hakola, H., Tarvainen, V., Bäck, J., Ranta, H., Bonn, B., Rinne, J., and Kulmala, M.: Seasonal variation of mono- and sesquiterpene emission rates of Scots pine, Biogeosciences, 3, 93–101, http://dx.doi.org/10.5194/bg-3-93-2006doi:10.5194/bg-3-93-2006, 2006b. Hakola, H., Hellén, H., Tarvainen, V., Bäck, J., Patokoski, J., and Rinne, J.: Annual variations of atmospheric VOC concentrations in a boreal forest, Boreal Environ. Res., 14, 722–730, 2009. Hari, P. and Kulmala, M.: Station for measuring ecosystem-atmosphere relations (SMEAR II), Boreal Environ. Res., 10, 315–322, 2005. Hellén, H., Hakola, H., Pirjola, L., Laurila, T., and Pystynen, K.-H.: Ambient air concentrations, source profiles and source apportionment of 71 different C<sub>2</sub>-C$_10$ volatile organic compounds at urban and residential areas in Finland, Environ. Sci. Technol., 40, 103–108, 2006. Hellén, H., Hakola, H., Haaparanta, S., Pietarila, H., and Kauhaniemi, M.: Influence of residential wood combustion on local air quality, Sci. Total Environ., 393, 283–290, 2008. Hellén, H., Kuronen, P., and Hakola, H.: Heated stainless steel tube for ozone removal in the ambient air measurements of mono- and sesquiterpenes, Atmos. Environ., 57, 35–40, 2012. Helmig, D., Revermann, T., Pollmann, J., Kaltschmidt, O., Hernandez, A. J., Bocquet, F., and David, D.: Calibration system and analytical considerations for quantitative sesquiterpene measurements in air, Journal of Chromatography A, 1002, 193–211, 2003. Hoffmann, T., Odum J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, 1997. Holzke, C., Hoffmann, T., Jaeger, L., Koppmann, R., and Zimmer, W.: Diurnal and seasonal variation of monoterpene and sesquiterpene emissions from Scots pine (Pinus sylvestris L.), Atmos. Environ., 40, 3174–3185, 2006. Janson, R.: Monoterpene emissions from Scots pine and Norwegian spruce, J. Geophys. Res., 98, 2839–2850, 1993. Jardine, K., Yañez Serrano, A., Arneth, A., Abrell, L., Jardine, A., van Haren, J., Artaxo, P., Rizzo, L. V., Ishida, F. Y., Karl, T., Kesselmeier, J., Saleska, S., and Huxman, T.: Within canopy sesquiterpene ozonolysis in Amazonia, J. Geophys. Res., 116, D19301, http://dx.doi.org/10.1029/2011JD016243doi:10.1029/2011JD016243, 2011. Jones, C. E., Hopkins, J. R., and Lewis, A. C.: In situ measurements of isoprene and monoterpenes within a south-east Asian tropical rainforest, Atmos. Chem. Phys., 11, 6971–6984, http://dx.doi.org/10.5194/acp-11-6971-2011doi:10.5194/acp-11-6971-2011, 2011. Kleinman, L. I.: The dependence of tropospheric ozone production rate on ozone precursors, Atmos. Environ., 39, 575–586, 2005. Kuhn, U., Rottemberger, S., Biesenthal, T., Wolf, A., Schebeske, G., Ciccioli, P., Brancaleoni, E., Frattoni, M., Tavares, T. M., and Kesselmeier, J.: Isoprene and monoterpene emissions of Amazonian tree species during the wet season: Direct and indirect investigations on controlling environmental functions, J. Geophys. Res., 107, 8071, http://dx.doi.org/10.1029/2001JD000978doi:10.1029/2001JD000978, 2002. Kulmala, M., Toivonen, A., Mäkelä, J. M., and Laaksonen, A.: Analysis of the growth of nucleation mode particles observed in Boreal forest, Tellus B, 50, 449–462, 1998. Kulmala, M., Kerminen, V.-M., Anttila, T., Laaksonen, A., and O'Dowd, C.: Organic aerosol formation via sulphate cluster activation, J. Geophys. Res., 109, D04205, http://dx.doi.org/10.1029/2003JD003961doi:10.1029/2003JD003961, 2004a. Kulmala, M., Suni, T., Lehtinen, K. E. J., Dal Maso, M., Boy, M., Reissell, A., Rannik, Ü., Aalto, P., Keronen, P., Hakola, H., Bäck, J., Hoffmann, T., Vesala, T., and Hari, P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, http://dx.doi.org/10.5194/acp-4-557-2004doi:10.5194/acp-4-557-2004, 2004b. Laurila T. and Hakola, H.: Seasonal Cycle of C2-C5 hydrocarbons over the Baltic Sea and Northern Finland, Atmos. Environ., 30, 1597–1607, 1996. Lappalainen, H. K., Sevanto, S., Bäck, J., Ruuskanen, T. M., Kolari, P., Taipale, R., Rinne, J., Kulmala, M., and Hari, P.: Day-time concentrations of biogenic volatile organic compounds in a boreal forest canopy and their relation to environmental and biological factors, Atmos. Chem. Phys., 9, 5447–5459, http://dx.doi.org/10.5194/acp-9-5447-2009doi:10.5194/acp-9-5447-2009, 2009. Liao, L., Dal Maso, M., Taipale, R., Rinne, J., Ehn, M., Junninen, H., Äijälä, M., Nieminen, T., Alekseychik, P., Hulkkonen, M., Worsnop, D. R., Kerminen, V.-M., and Kulmala, M.: Monoterpene pollution episodes in a forest environment: indication of anthropogenic origin and association with aerosol particles, Boreal Environ. Res., 16, 288–303, 2011. Ortega J., Helmig, D., Guenther, A., Harley, P., Pressley, S., and Vogel, C.: Flux estimates and OH reaction potential of reactive biogenic volatile organic compounds (BVOCs) from a mixed northern hardwood forest, Atmos. Environ., 41, 5479–5495, 2007. Rinne, J., Hakola, H., Laurila, T., and Rannik, Ü.: Canopy scale monoterpene emissions of Pinus sylvestris dominated forests, Atmos. Environ., 34, 1099–1107, 2000. Rinne, H. J. I., Guenther, A. B., Greenberg, J. P., and Harley, P. C.: Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature, Atmos. Environ., 36, 2421–2426, 2002. Rinne, J., Ruuskanen, T. M., Reissell, A., Taipale, R., Hakola, H., and Kulmala, M.: On-line PTR-MS measurements of atmospheric concentrations of volatile organic compounds in a European boreal forest ecosystem, Boreal Environ. Res., 10, 425–436, 2005. Rinne, J., Bäck, J., and Hakola, H.: Biogenic volatile organic compound emissions from the Eurasian taiga: current knowledge and future directions, Boreal Environ. Res., 14, 807–826, 2009. Ruuskanen, T. M., Kajos, M., Hellén, H., Hakola, H., Tarvainen, V., and Rinne, J.: Volatile organic compound emissions from Siberian larch, Atmos. Environ., 41, 5807–5812, 2007. Seco, R., Peñuelas, J., Filella, I., Llusià, J., Molowny-Horas, R., Schallhart, S., Metzger, A., Müller, M., and Hansel, A.: Contrasting winter and summer VOC mixing ratios at a forest site in the Western Mediterranean Basin: the effect of local biogenic emissions, Atmos. Chem. Phys., 11, 13161–13179, http://dx.doi.org/10.5194/acp-11-13161-2011doi:10.5194/acp-11-13161-2011, 2011. Shu, Y. and Atkinson, R.: Atmospheric lifetimes and fates of a series of sesquiterpenes, J. Geophys. Res., 100, 7275–7281, 1995. Sillman, S.: The relation between ozone, NO$_x$ and hydrocarbons in urban and polluted rural environments, Atmos. Environ., 33, 1821–1845, 1999. Taipale, R., Kajos, M. K., Patokoski, J., Rantala, P., Ruuskanen, T. M., and Rinne, J.: Role of de novo biosynthesis in ecosystem scale monoterpene emissions from a boreal Scots pine forest, Biogeosciences, 8, 2247–2255, http://dx.doi.org/10.5194/bg-8-2247-2011doi:10.5194/bg-8-2247-2011, 2011. Tarvainen, V., Hakola, H., Hellén, H., Bäck, J., Hari, P., and Kulmala, M.: Temperature and light dependence of the VOC emissions of Scots pine, Atmos. Chem. Phys., 5, 989–998, http://dx.doi.org/10.5194/acp-5-989-2005doi:10.5194/acp-5-989-2005, 2005. Tarvainen, V., Hakola, H., Rinne, J., Hellén, H., and Haapanala, S.: Towards a comprehensive emission inventory of terpenoids from boreal ecosystems, Tellus, 59B, 526–534, 2007. Tunved, P., Hansson, H.-C., Kerminen, V.-M., Ström, J., Dal Maso, M., Lihavainen, H., Viisanen, Y., Aalto, P. P., Komppula, M., and Kulmala, M.: High natural aerosol loading over Boreal forests, Science, 312, 261–263, 2006. Yassaa, N. and Williams, J.: Analysis of enantiomeric and nonenantiomeric monoterpenes in plant emissions using portable dynamic air sampling/solid-phase microextraction (PDASSPME) and chiral gas chromatography/mass spectrometry, Atmos. Environ., 39, 4875–4884, 2005. Yassaa, N. and Williams, J.: Enantiomeric monoterpene emissions from natural and damaged Scots pine in a boreal coniferous forest measured using solid-phase microextraction and gas chromatography/mass spectrometry, J. Chromatogr. A., 1141, 138–144, http://dx.doi.org/10.1016/J.Chroma.2006.12.006doi:10.1016/J.Chroma.2006.12.006, 2007. Yassaa, N., Brancaleoni, E., Frattoni, M., and Ciccioli, P.: Trace level determination of enantiomeric monoterpenes in terrestrial plant emission and in the atmosphere using a β-cyclodextrin capillary column coupled with thermal desorption and mass spectrometry, J. Chromatogr. A, 915, 185–197, 2001. Williams, J., Yassaa, N., Bartenbach, S., and Lelieveld, J.: Mirror image hydrocarbons from Tropical and Boreal forests, Atmos. Chem. Phys., 7, 973–980, http://dx.doi.org/10.5194/acp-7-973-2007doi:10.5194/acp-7-973-2007, 2007.